Ryan J. Anderson, Rachel L. Fine, Rachel M. Rapagnani and Ian A. Tonks*,
{"title":"二氧化碳衍生的δ-戊内酯与ε-己内酯和 l-内酯的开环共聚物","authors":"Ryan J. Anderson, Rachel L. Fine, Rachel M. Rapagnani and Ian A. Tonks*, ","doi":"10.1021/acs.macromol.4c00770","DOIUrl":null,"url":null,"abstract":"<p >Ring-opening random, gradient, and block copolymerizations of CO<sub>2</sub>-derived δ-valerolactone 3-ethyl-6-vinyltetrahydro-2<i>H</i>-pyran-2-one (EtVP) with ε-caprolactone (ε-CL) and <span>l</span>-lactide (LLA) are reported. By employing both concurrent and sequential addition strategies, we could access a variety of thermal and physical properties. Concurrent copolymerization of EtVP with ε-CL yielded gradient copolymers with low glass transition temperatures, while block copolymerizations via sequential addition led to semicrystalline materials regardless of monomer feed ratios. For LLA copolymerizations, glass transition temperatures increased with LLA incorporation regardless of the addition method, but higher <i>T</i><sub>g</sub> values were observed in block copolymerizations from sequential addition. Tensile testing of <i>poly</i>(EtVP-<i>b</i>-LLA) with a molar ratio of 40:60 EtVP:LLA resulted in σ = 0.8 MPa, <i>E</i> = 5.6 MPa, and 83% elongation at break. The chemical recyclability of EtVP-based copolymers was explored as an end-of-life option. Both ε-CL and LLA copolymers could be recycled, with block copolymers giving higher yields of recycled monomers than random copolymers.</p>","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":null,"pages":null},"PeriodicalIF":5.1000,"publicationDate":"2024-06-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Ring-Opening Copolymerizations of a CO2-Derived δ-Valerolactone with ε-Caprolactone and l-Lactide\",\"authors\":\"Ryan J. Anderson, Rachel L. Fine, Rachel M. Rapagnani and Ian A. Tonks*, \",\"doi\":\"10.1021/acs.macromol.4c00770\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >Ring-opening random, gradient, and block copolymerizations of CO<sub>2</sub>-derived δ-valerolactone 3-ethyl-6-vinyltetrahydro-2<i>H</i>-pyran-2-one (EtVP) with ε-caprolactone (ε-CL) and <span>l</span>-lactide (LLA) are reported. By employing both concurrent and sequential addition strategies, we could access a variety of thermal and physical properties. Concurrent copolymerization of EtVP with ε-CL yielded gradient copolymers with low glass transition temperatures, while block copolymerizations via sequential addition led to semicrystalline materials regardless of monomer feed ratios. For LLA copolymerizations, glass transition temperatures increased with LLA incorporation regardless of the addition method, but higher <i>T</i><sub>g</sub> values were observed in block copolymerizations from sequential addition. Tensile testing of <i>poly</i>(EtVP-<i>b</i>-LLA) with a molar ratio of 40:60 EtVP:LLA resulted in σ = 0.8 MPa, <i>E</i> = 5.6 MPa, and 83% elongation at break. The chemical recyclability of EtVP-based copolymers was explored as an end-of-life option. Both ε-CL and LLA copolymers could be recycled, with block copolymers giving higher yields of recycled monomers than random copolymers.</p>\",\"PeriodicalId\":51,\"journal\":{\"name\":\"Macromolecules\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":5.1000,\"publicationDate\":\"2024-06-18\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Macromolecules\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://pubs.acs.org/doi/10.1021/acs.macromol.4c00770\",\"RegionNum\":1,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"POLYMER SCIENCE\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Macromolecules","FirstCategoryId":"92","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acs.macromol.4c00770","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"POLYMER SCIENCE","Score":null,"Total":0}
Ring-Opening Copolymerizations of a CO2-Derived δ-Valerolactone with ε-Caprolactone and l-Lactide
Ring-opening random, gradient, and block copolymerizations of CO2-derived δ-valerolactone 3-ethyl-6-vinyltetrahydro-2H-pyran-2-one (EtVP) with ε-caprolactone (ε-CL) and l-lactide (LLA) are reported. By employing both concurrent and sequential addition strategies, we could access a variety of thermal and physical properties. Concurrent copolymerization of EtVP with ε-CL yielded gradient copolymers with low glass transition temperatures, while block copolymerizations via sequential addition led to semicrystalline materials regardless of monomer feed ratios. For LLA copolymerizations, glass transition temperatures increased with LLA incorporation regardless of the addition method, but higher Tg values were observed in block copolymerizations from sequential addition. Tensile testing of poly(EtVP-b-LLA) with a molar ratio of 40:60 EtVP:LLA resulted in σ = 0.8 MPa, E = 5.6 MPa, and 83% elongation at break. The chemical recyclability of EtVP-based copolymers was explored as an end-of-life option. Both ε-CL and LLA copolymers could be recycled, with block copolymers giving higher yields of recycled monomers than random copolymers.
期刊介绍:
Macromolecules publishes original, fundamental, and impactful research on all aspects of polymer science. Topics of interest include synthesis (e.g., controlled polymerizations, polymerization catalysis, post polymerization modification, new monomer structures and polymer architectures, and polymerization mechanisms/kinetics analysis); phase behavior, thermodynamics, dynamic, and ordering/disordering phenomena (e.g., self-assembly, gelation, crystallization, solution/melt/solid-state characteristics); structure and properties (e.g., mechanical and rheological properties, surface/interfacial characteristics, electronic and transport properties); new state of the art characterization (e.g., spectroscopy, scattering, microscopy, rheology), simulation (e.g., Monte Carlo, molecular dynamics, multi-scale/coarse-grained modeling), and theoretical methods. Renewable/sustainable polymers, polymer networks, responsive polymers, electro-, magneto- and opto-active macromolecules, inorganic polymers, charge-transporting polymers (ion-containing, semiconducting, and conducting), nanostructured polymers, and polymer composites are also of interest. Typical papers published in Macromolecules showcase important and innovative concepts, experimental methods/observations, and theoretical/computational approaches that demonstrate a fundamental advance in the understanding of polymers.